Synthesis of new copper(I) based linear 1-D-coordination polymers with neutral imidazolinium-dithiocarboxylate ligands

Article abstract of DOI:10.1039/c4ra09033k

An imidazolinium-dithiocarboxylate betaine has been applied for the first time as a ligand in a coordination polymer with copper(i) halides. The resulting 1-D-coordination compounds show a linear double chain structure with trigonally coordinated copper(i

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COMMUNICATION
Synthesis of New Copper(I) Based Linear 1-D-
Coordination Polymers with Neutral Imidazolinium-
Dithiocarboxylate Ligands
Cite this: DOI: 10.1039/x0xx00000x
a
a
b
b
a
a
Received 00th January 2012,
Accepted 00th January 2012
A. Neuba,* J. Ortmeyer, D. D. Konieczna, G. Weigel, U. Flörke, G. Henkel and
b
R. Wilhelm*
DOI: 10.1039/x0xx00000x
www.rsc.org/
An imidazolinium-dithiocarboxlyate betaine has been applied to a better understanding of the properties of these betaines, we
present here their application as neutral ligands for the preparation of
copper(I) based 1D-coordination polymers.
for the first time as a ligand in a coordination polymer with
copper(I) halides. The resulting 1D-coordination compounds
show
a linear double chain structure with trigonally
Coordination polymers represent an increasingly important class of
new functional materials, and the number of publications has
coordinated copper(I). The potential of the material as a
heterogeneous photocatalyst was explored.
12
increased exponentially since the mid 1990ties. This is due to their
13
14
15
high potential in magnetic materials, catalysis, gas sorption,
16
17
Imidazol(in)ium-dithiocarboxylate betaines (NHC·CS ) are formal sensing and optoelectronics. In the present study, the potential of
2
adducts of a corresponding imidazol(in)ium carbene and CS . The the new material was investigated as a heterogeneous photocatalyst.
2
plane of the negatively charged CS group is almost perpendicular to
2
10
the positively charged imidazolium ring. Compared to their CO and Our approach starts with the synthesis (Scheme 1) of the betaine
2
1
1-2
COS analogues, the CS betaines are known to be stable. After Bz ImCS2 (1) and the determination of its hitherto unknown
2
2
these betaines were described for the first time by Winberg and molecular structure (Figure 1) for
a comparative structural
3
Coffmann, several groups focused their interests towards their discussion with copper complexes derived thereof.
chemical behaviour, for example in [3+2] cycloadditions with
4
electron deficient alkynes. Their application as ligands resulted in
5
several reported metal complexes. The latter were investigated in a
6
few catalytic reactions. Moreover, Delaude et al. have shown that
stereoelectronic parameters of N-heterocyclic carbenes can be
determined via XRD analysis of their CS2 adducts due to their
7
outstanding ability to crystallize.
Based on our interest in these betains, we have recently shown that
Scheme 1 Synthesis of the betaine Bz ImCS (1).
2
2
symmetric imidazolinium-dithiocarboxylates can successfully
8
applied as organocatalysts for the TMSCN addition on aldehydes
Molecules of 1 show equal C-S and C-N bond lengths of 1.669(1)
and 1.321(1) Å, respectively, and S-C-S as well as N-C-N valence
angles of 123.5(1) and 112.8(1)° (Table 1). The CS /CN planes
and enantiopure analogues as organocatalysts for an asymmetric
9
Staudinger reaction. Furthermore, we were able to synthesize a
2
2
novel class of ionic liquids via methylation of the corresponding
betaines. Spectroscopic analysis showed that the resulting red
cations have different absorption maxima depending on the solvent
deviate significantly from an orthogonal arrangement exhibiting a
dihedral angle of 79.3°. These parameters are comparable to
structural data of other crystallised betaines with aromatic and
aliphatic N substituents with dihedral angles ranging from 76.5 to
10
and the lipophilicity of the corresponding counter anions. More
recently, we reported the application of NHC·CS as colorimetric
4c, 4e, 7, 18
2
87.9°.
2
+
+ 11
chemosensors for the detection of Hg and Ag . As a contribution
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To the best of our knowledge, 2 and 3 are the first imidazolinium
dithiocarboxylate copper complexes known so far. Coordination
polymers with other dithiocarboxylates and copper are also not
1
9
known. In this context it should be mentioned that several mono -
1
9h, 20
and polynuclear
copper dithiocarboxylate complexes as well as
2
1
other dithiocarboxylate compounds with metals such as gold,
manganese, cadmium and mercury have been described.
22
23
24
Figure 1 Molecular structure of 1 in the crystalline state.†
S
S
N
Bn
Cu
X
N
S
S
CuX
Bn
Bn
N
MeCN
N
n
Bn
[
CuCl(Bz ImCS )]
2 2 n
(2)
(3)
1
[CuBr(Bz ImCS )]
2 2 n
Scheme 2 Synthesis of Cu(I) coordination polymers (X = Cl, Br).
Figure 3 Crystal packing of 2 and 3 viewed along with
intermolecular Cbenzyl-H…S contacts shown as dotted lines. H-atoms
not involved in bonding are omitted
Reaction of 1 with CuX (X = Cl, Br) in acetonitrile (Scheme 2) leads
to deep coloured (red, X = Cl; brown, X = Br) suspensions, from
which after filtration and subsequent treatment with diethyl ether
brown (X = Cl) or orange (X = Br) crystals separate in the course of
a few days. Interestingly, X-ray diffraction studies revealed that
compounds 2 and 3 are coordination polymers of composition
Table 1 Selected bond lengths /Å and angles /° for
1,
2
and
3.
Atoms
1
Bond length
Atoms
Angle
[
CuX(Bz ImCS )] , in which single 1D-chains are formed by
2 2 n
alternately arranged {CuX} units and betaine ligands (Figure 2).
S1 - C1
C1 - C2
C2 - N1
N1 - C3
C3 - C3A
1.669(1)
1.493(2)
1.321(1)
1.470(2)
1.530(3)
S1 - C1 - S1A
S1 - C1 - C2
C1 - C2 - N1
N1 - C2 - N1A
C2 - N1 - C3
N1 - C3 - C3A
130.68(10)
114.66(5)
124.01(8)
111.97(15)
110.98(11)
102.92(7)
2
Cu1 - S1
2.244(1)
S1 - Cu1 - S2A
S1 - Cu1 - Cl1
S2A - Cu1 - Cl1
C4 - S1 - Cu1
C4 - S2 - Cu1A
S1 - C4 - S2
107.41(3)
126.89(3)
125.66(3)
112.77(10)
113.52(11)
124.18(18)
117.9(2)
Cu1 - S2A 2.243(1)
Cu1 - Cl1
C4 - S1
C4 - S2
C1 - C4
C1 - N1
C1 - N2
2.194(1)
1.682(3)
1.678(3)
1.482(4)
1.317(4)
1.322(3)
S1 - C4 - C1
S2 - C4 - C1
117.9(2)
C4 - C1 - N1
C4 - C1 - N2
N1 - C1 - N2
123.8(3)
Figure 2 Section of the structure of 2 in the crystalline state.†
124.0(3)
Both coordination polymers crystallise isostructural in the triclinic
space group P-1 with Cu(I) atoms adopting trigonal-planar
112.2(2)
3
coordination geometries within their S X donor sets (mean valence
2
Cu1 - S1
2.244(5)
S1 - Cu1 - S2A
S1 - Cu1 - Br1
S2A - Cu1 - Br1
C4 - S1 - Cu1
C4 - S2- Cu1A
S1 - C4 - S2
110.53(2)
125.39(1)
124.02(2)
114.49(5)
115.11(5)
123.55(9)
118.50(11)
117.95(11)
123.45(13)
123.78(13)
112.78(13)
angle 119.99° within 2 and 119.98° within 3; see Table 1). The Cu-S
bonds are equal in lengths and average to 2.244 Å in both 2 and 3.
Pairs of polymeric chains are linked via intermolecular Cbenzyl-H…S
interactions with H…S distances of 2.84 (2) and 2.79 Å (3) and C-
H…S angles of 141.9(2) (2) and 143.5(1)° (3) to form endless
double chains (Figure 3). Interestingly, the bond lengths within the
Cu1 - S2A 2.245(4)
Cu1 - Br1
C4 - S1
C4 - S2
C1 - C4
C1 - N1
C1 - N2
2.323(3)
1.680(2)
1.683(2)
1.487(2)
1.319(2)
1.316(2)
CS and CN units of the coordinated and free betaine show no
2
2
S1 - C4 - C1
S2 - C4 - C1
C4 - C1 - N1
C4 - C1 - N2
N1 - C1 - N2
significant differences (Table 1). Only the S-C-S bond angles
contract from 130.7(1) to 124.1(2)° in 2 and to 123.5(1)° in 3.
Furthermore, the CS /CN planes are now nearly orthogonally
2
2
arranged with dihedral angles of 87.1° in both coordination
polymers.
2
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DOI: 10.1039/C4RA09033K
The one-dimensional chain within crystals of 2 and 3 consisting of
2
alternating Cu(I) and sp hybridized negatively charged CS units
2
define an infinite 1-dimensional d-π system. Taking into account that
Acknowledgment
copper containing 1D coordination polymers have shown potential
25
as catalysts and have been applied as photoactive material for dye-
2
6
sensitized solar cells, it was decided to investigate the potential of We would like to thank the German research council (DFG)
the new material as heterogeneous photocatalyst in case of a thiol- and the German Federal Ministry of education and research
ene reaction. This reaction is of exceptional importance because of (BMBF) for the continuous support of our work. D. Konieczna
27
its wide spectrum of applications in synthetic sulphur chemistry. In and J. Ortmeyer thank the Evonik Foundation and Fonds der
a preliminary study, the addition of thiophenol to styrene was Chemischen Industrie (FCI) for granting doctoral fellowships
explored with white light (Scheme 3). This reaction has been for each.
2
+
example catalysed with the photocatalyst Ru(bpz)3
under
2
8
homogenous conditions. However, the application of reusable
heterogeneous systems based on low-cost and better biocompatible
metals would be beneficial.
Notes and references
a
University of Paderborn, Department of Chemistry, Inorganic Chemistry
Section, Warburgerstr. 100, 33098 Paderborn, Germany. Fax: +49 5251
6
b
03319; Tel: +49 5251 602165; E-mail: adam.neuba@uni-paderborn.de.
University of Paderborn, Department of Chemistry, Organic Chemistry
Section, Warburgerstr. 100, 33098 Paderborn, Germany. Fax: +49 5251
6
†
03245; Tel: +49 5251 605766; E-mail: rene.wilhelm@uni-paderborn.de.
Anisotropic displacement ellipsoids are drawn at the 50% probability
level. CCDC-1008787, 1000389 and 1000390 contain the supplementary
crystallographic data for and , respectively. These data can be
Scheme 3 Catalysed thiol-ene reaction of thiophenol with styrene.
1,
2
3
The existence of 2 and 3 is restricted to the crystalline state. Any obtained free of charge via
attempts to dissolve the compounds are expected to result in http://www.ccdc.cam.ac.uk/conts/retrieving.html, or from the Cambridge
depolymerisation reactions ESI-MS and NMR analysis (see
Supplementary Information figures S1-S4) of solutions obtained
from reactions of 2 and 3 with dimethylsulfoxide or methanol
confirm the formation of the mononuclear complexes
Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ,
UK; fax: (+44) 1223 336 033; or e-mail: deposit@ccdc.cam.ac.uk.
Electronic Supplementary Information (ESI) available: Experimental
procedures and spectral data. See DOI: 10.1039/c000000x/
+
-
[
Cu(Bn ImCS ) ] [CuX ] (X = Cl, Br). This observation supports
2 2 2 2
our assumption that a breakup of the 1-D-coordination polymer took
place on solvent attack. The stability of 2 and 3 towards acetonitrile
allowed for probing the crystals as heterogenic catalyst. In case of 2
the formation of the photoproduct in 60% yield after 40 h was
observed. A control reaction in the absence of light gave a yield of
1
2
3
4
(a) W. Kirmse, Eur. J. Org. Chem., 2005, 237; (b) L. Delaude,
Eur. J. Inorg. Chem., 2009, 1681.
(a) J. Nakayama, J. Syn. Org. Chem. Jpn., 2002, 60, 106; (b)
Sulfur Lett., 1993, 15, 239.
H. E. Winberg and D. D. Coffman, J. Am. Chem. Soc., 1965, 87,
2
3%, while under light conditions in the absence of crystalline 2 a
2
776.
yield of 34% was found. When the reaction was carried out with a
solution obtained from 2 (and dichloromethane), no catalytic activity
was found, again suggesting that the electronic properties of the
intact copper coordination polymer in the solid state are essential for
the catalytic activity. Compound 3 showed no activity. A difference
in the catalytic activity of different halide ligands on transition metal
(a) W. Schössler and M. Regitz, Chem. Ber., 1974, 104, 1931; (b)
W. Krasuski, D. Nikolaus and M. Regitz, Liebigs Ann. Chem.,
1982, 1451; (c) W. S. Sheldrick, A. Schönberg, E. Singer and E.
Eckert, Chem. Ber., 1980, 113, 3605; (d)
D. H. Clemens, A. J.
Bell and J. L. O'Brien, Tetrahedron Lett., 1965, 6, 3257; (e) N.
Kuhn, H. Bohnen and G. Henkel, Z. Naturforsch., 1994, 49b,
1
473; (f) J. Nakayma and I. Akiyma, J. Chem. Soc., Chem.
29
complexes is rare but no unknown and cannot always be predicted.
Commun., 1992, 1522; (g) A. Nagasawa, I. Akiyama, S. Mashima
and J. Nakayama, Heteroatom Chem., 1995, 6, 45; (h) K.
Akimoto and J. Nakayama, Heteroatom Chem., 1997, 8, 505; (i)
L. L. Borer, J. V. Kong and D. E. Oram, Acta Crystallogr., Sect.
C, 1989, 45, 1169; (j) T. Fujihara, T. Ohba, A. Nagasawa, J.
Nakayama and K. Yoza, Acta Crystallogr. C, Sect. C, 2002, 58,
o558; (k) J. Nakayama, T. Otani, T. Tadokoro, Y. Sugihara and A.
Ishii, Chem. Lett., 2001, 768; (l) T. Otani, Y. Sugihara, A. Ishii
and J. Nakayama, Heteroatom Chem., 1998, 9, 703; (m) N. Kuhn,
G. Weyers and G. Henkel, Chem. Commun., 1997, 627; (n) N.
Kuhn, G. Weyers, S. Dummling and B. Speiser, Phosphorus,
Sulfur Silicon Relat. Elem., 1997, 128, 45; (o) S. Dummling, B.
Speiser, N. Kuhn and G. Weyers, Acta Chim. Scand. , 1999, 53,
876; (p) J. Nakayama, T. Otani, Y. Sugihara and A. Ishii, Chem.
Lett., 1998, 321; (q) J. Nakayama, L. Zhao, T. Otani, Y. Sugihara
and A. Ishii, Chem. Lett., 2000, 1248.
(a) M. L. Ziegler, H. Weber, B. Nuber and O. Serhadle, Z.
Naturforsch. B, 1987, 42b, 1411; (b) M. L. Ziegler, K.
Blechschmitt, H. Bock, E. Guggolz and R. P. Korswagen, Z.
Naturforsch. B, 1988, 43, 590; (c) S. R. Banerjee, A. Nagasawa
and J. Zubieta, Inorg. Chim. Acta, 2002, 340, 155; (d) L. L. Borer,
J. V. Kong, P. A. Keihl and D. M. Forkey, Inorg. Chim. Acta,
1987, 129, 223; (e) L. L. Borer, J. Kong and E. Sinn, Inorg. Chim.
Acta, 1986, 122, 145; (f) I. Miyashita, K. Matsumoto, M.
Although the catalytic activity of compound 2 is moderate, this is the
first example of a coordination polymer containing copper suited as
a heterogeneous photo-redox catalyst.
Conclusions
In conclusion, an imidazolinium-dithiocarboxylate has been
applied for the first time as a ligand towards copper(I) halides.
The resulting 1-D coordination polymers
structure with {CuX} units attached to negatively charged CS2
donor groups of the betaine resulting in an infinite d- system.
2 and 3 show a linear
π
The potential of the material as heterogeneous photocatalyst
was shown in a radical thiol-ene reaction for the first time.
Presently we investigate the catalytic activity of our material
with other thiols and try to optimize the reaction conditions also
by using other imidazolinium-dithiocarboxlyates. Besides
investigations directed towards stereoselective photoredox
5
reactions, the use as dyes in TiO based photovoltaic cells is
2
explored as well.
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Kobayashi, A. Nagasawa and J. Nakayama, Inorg. Chim. Acta,
998, 283, 256; (g) U. Siemeling, H. Memczak, C. Bruhn, F.
Vogel, F. Traeger, J. E. Baio and T. Weidner, Dalton Trans., 21
012, 41, 2986; (h) S. Naeem, L. Delaude, A. J. P. White and J.
D. E. T. Wilton-Ely, Inorg. Chem., 2010, 49, 1784; (i) S. Naeem,
A. L. Thompson, A. J. P. White, L. Delaude and W. E. Lionel, 22
Dalton Trans., 2011, 40, 3737; (j) T. Sugaya, T. Fujihara, A.
Baenziger, R. Pedelty, M. L. Caffery and S. Kanodia, Inorg.
Chem., 1989, 28, 2829.
M.-R. Azani, O. Castillo, M. L. Gallego, T. Parella, G. Aullón, O.
Crespo, A. Laguna, S. Alvarez, R. Mas-Ballesté and F. Zamora,
Chem. Eur. J., 2012, 18, 9965.
1
2
M. Ciampolini, C. Mengozzi and P. Orioli, J. Chem. Soc. Dalton,
1975, 2051.
Nagasawa and K. Unoura, Inorg. Chim. Acta, 2009, 362, 4813.
(a) T. Sugaya, T. Ohba, F. Sai, S. Mashima, T. Fujihara, K.
23
V. G. Young and E. R. T. Tiekink, Acta Crystallogr., Sect. E,
2002, 58, m537.
6
7
Unoura and A. Nagasawa, Organometallics, 2013, 32, 3441; (b) 24
L. Delaude, X. Sauvage, A. Demonceau and J. Wouters,
Organometallics, 2009, 28, 4056; (c) M. J. D. Champion, R. 25
Solanki, L. Delaude, A. J. P. White and J. D. E. T. Wilton-Ely,
A. M. Bond, R. Colton, A. F. Hollenkamp, B. F. Hoskins and K.
McGregor, J. Am. Chem. Soc., 1987, 109, 1969.
J. García-Álvarez, J. Díez, J. Gimeno, F. J. Suárez and C. Vincent,
Eur. J. Inorg. Chem., 2012, 5854.
N. Tanaka, T. Okubo, H. Anma, K. H. Kim, Y. Inuzuka, M.
Maekawa and T. Kuroda-Sowa, Eur. J. Inorg. Chem., 2013, 3384.
A. Gress, A. Volkel and H. Schlaad, Macromolecules, 2007, 40,
7928.
(a) E. L. Tyson, M. S. Ament and T. P. Yoon, J. Org. Chem.,
2013, 78, 2046; (b) M. H. Keylor, J. E. Park, C.-J. Wallentin and
C. R. J. Stephenson, Tetrahedron, 2014, 70, 4264; (c) E. L.
Tyson, Z. L. Niemeyer and T. P. Yoon, J. Org. Chem., 2014, 79,
1427.
(a) K. Fagnou and M. Lautens, Angew. Chem. Int. Ed. , 2002, 41,
26; (b) S. L. Zhang and Y. Q. Ding, Organometallics, 2011, 30,
633; (c) L. W. Mapson, Biochem J., 1945, 39, 228; (d) S.-L.
Zhang, L. Liu, Y. Fu and Q.-X. Guo, Organometallics, 2007, 26,
4546; (e) W. Mo, H. Xiong, J. Hu, Y. Ni and G. Li, Appl.
Organometal. Chem., 2010, 24, 576; (f) A. Jutand, Appl.
Organometal. Chem., 2004, 18, 574; (g) P. A. Evans, D. K. Leahy
and L. M. Slieker, Tetrahedron: Asymmetry, 2003, 14, 3613; (h)
P. A. Evans and D. K. Leahy, J. Am. Chem. Soc., 2002, 124, 7882.
Dalton Trans., 2012, 41, 12386.
26
L. Delaude, A. Demonceau and J. Wouters, Eur. J. Inorg. Chem.,
2
009, 1882.
A. Blanrue and R. Wilhelm, Synlett, 2004, 2621.
O. Sereda, A. Blanrue and R. Wilhelm, Chem. Commun., 2009, 28
040.
27
8
9
1
1
1
0
1
A. Blanrue and R. Wilhelm, Synthesis, 2009, 583.
D. D. Konieczna, A. Blanrue and R. Wilhelm, Z. Naturforsch.,
2
014, 69b, 596.
S.-Y. Zhang, Z. Zhang and M. J. Zaworotko, Chem. Commun., 29
013, 49, 9700.
(a) D. Maspoch, D. Ruiz-Molina and J. Veciana, J. Mat. Chem.,
004, 14, 2713; (b) C. Zhang, Y. Chen, H. Ma, T. Yu, B. Liu and
1
1
2
3
2
2
H. Pang, New J. Chem., 2013, 37, 1364; (c) X. Wang, X.-B. Li,
R.-H. Yan, Y.-Q. Wang and E.-Q. Gao, Dalton Trans., 2013, 42,
1
0000; (d) P. Amo-Ochoa, O. Castillo and F. Zamora, Dalton
Trans., 2013, 42, 13453.
(a) A. Corma, H. García and F. X. L. i. Xamena, Chem. Rev.,
1
1
4
5
2
010, 110, 4606; (b) D. Farrusseng, S. Aguado and C. Pinel,
Angew. Chem. Int. Ed., 2009, 48, 7502; (c) J. Lee, O. F. Fartha, J.
Roberts, K. A. Scheidt, S. T. Nguyen and J. T. Hupp, Chem. Soc.
Rev., 2009, 38, 1450; (d) J. Garcia-Álvarez, J. Díez, C. Vidal and
C. Vicent, Inorg. Chem., 2013, 52, 6533.
(a) L. J. Murray, M. Dincá and J. R. Long, Chem. Soc. Rev., 2009,
3
8, 1294; (b) J. L. C. Rowsell and O. M. Yaghi, Angew. Chem.
Int. Ed., 2005, 44, 4670; (c) B. Chen, S. Xiang and G. Qian, Acc.
Chem. Res., 2010, 43, 1115.
1
1
6
7
M. A. Green, Nature Mater., 2010, 9, 539.
R. Siebert, A. Winter, M. Schmitt, J. Popp, U. S. Schubert and B.
Dietzek, Macromol. Rapid Commun., 2012, 33, 481.
N. Kuhn, E. Niquet, M. Steinmann and I. Walker, Z. Naturforsch.,
1
1
8
9
1
999, 54b, 1181.
(a) T. C. Deivaraj and J. J. Vittal, Acta Crystallogr., Sect. E, 2001,
7, m566; (b) D. F. Zigler, E. Tordin, G. Wu, A. Iretski, E. Cariati
5
and P. C. Ford, Inorg. Chim. Acta, 2011, 374, 261; (c) I. Garcia-
Orozco, J. G. Lopez-Cortes, M. C. Ortega-Alfaro, R. A. Toscano,
G. Penieres-Carrillo and C. Alvarez-Toledano, Inorg. Chem.,
2
1
004, 43, 8572; (d) H. Otto and H. Werner, Chem. Ber., 1987,
20, 97; (e) M. Pellei, S. Alidori, M. Camalli, G. Campi, G. G.
Lobbia, M. Mancini, G. Papini, R. Spagna and C. Santini, Inorg.
Chim. Acta, 2008, 361, 1456; (f) M. Kondo, E. Shimizu, T.
Horiba, H. Tanaka, Y. Fuwa, K. Nabari, K. Unoura, T. Naito, K.
Maeda and F. Uchida, Chem. Lett., 2003, 32, 944; (g) A. Camus,
N. Marsich and G. Nardin, J. Organomet. Chem., 1980, 188, 389;
(h) A. Camus, N. Marsich, A. M. M. Lanfredi and F. Ugozzoli,
Inorg. Chim. Acta, 1989, 161, 87; (i) P. Strauch, B. Dempe, R.
Kempe, W. Dietzsch, J. Sieler and E. Hoyer, Z. Anorg. Allg.
Chem., 1994, 620, 498; (j) J. Vicente, P. Gonzalez-Herrero, Y.
Garcia-Sanchez, P. G. Jones and D. Bautista, Eur. J. Inorg.
Chem., 2006, 115.
2
0
(a) A. M. M. Lanfredi, F. Ugozzoli, A. Camus and N. Marsich,
Inorg. Chim. Acta, 1985, 99, 111; (b) A. M. M. Lanfredi, A.
Tiripicchio, A. Camus and N. Marsich, J. Chem. Soc. Dalton,
1
989, 753; (c) I. Bassanetti, M. Gennari, L. Marchio, M. Terenghi
and L. Elviri, Inorg. Chem., 2010, 49, 7007; (d) M. Biagini-Cingi,
A. M. M. Lanfredi, F. Ugozzoli, A. Camus and N. Marsich, Inorg.
Chim. Acta, 1997, 262, 69; (e) D. Coucouvanis, D. Swenson, N.
C. Baenziger, R. Pedelty and M. L. Caffery, J. Am. Chem. Soc.,
1
977, 99, 8097; (f) D. Coucouvanis, D. Swenson, N. C.
4
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